WO2013062304A1

WO2013062304A1 - Apparatus and method for reducing carbon dioxide using solar light

Info

Publication number: WO2013062304A1
Application number: PCT/KR2012/008754
Authority: WO
Inventors: 윤경병
Original assignee: 서강대학교산학협력단
Priority date: 2011-10-24
Filing date: 2012-10-24
Publication date: 2013-05-02
Also published as: US9364808B2; US20140235736A1

Abstract

The present application relates to an apparatus and method for reducing carbon dioxide using solar light.

Description

Reduction Apparatus and Reduction Method of Carbon Dioxide Using Solar Light

The present application relates to a reduction apparatus and a reduction method of carbon dioxide using sunlight.

Photosynthesis uses sunlight as energy to convert carbon dioxide and water into oxygen and starch. This photosynthesis is actively occurring in green plants and photosynthetic bacteria. In response to the photosynthesis of nature, the reaction of converting carbon dioxide and water into oxygen, liquid fuel, etc. using sunlight as energy is called artificial photosynthesis.

In chemical terms, carbon dioxide (CO ₂ ) and water (H ₂ O) are materials with very low potential energy, and fuel and oxygen are materials with relatively high potential energy. Plants in nature use solar energy to convert carbon dioxide and water into carbohydrates and oxygen (O ₂ ), which are higher potential energy, through photosynthesis. When the converted carbohydrate and oxygen are reacted again, they are converted into carbon dioxide and water and heat is released to the outside by the difference in potential energy of the two reactants.

On the other hand, human beings are getting energy through the combustion of fossil fuels, that is, by reacting fossil fuels with oxygen to produce carbon dioxide and water. As a result, the concentration of carbon dioxide in the atmosphere is increasing day by day and is considered to be a major cause of global warming. The global warming, which is currently progressing rapidly, is recognized as one of the major causes of global environmental problems. Therefore, efforts are being made worldwide to improve the utilization of renewable energy such as solar energy, hydropower, wind power, tidal power, geothermal energy, and biofuel instead of fossil fuel. The most promising renewable energy is solar energy.

Conventionally developed methods for utilizing solar energy include a method of converting solar heat and sunlight into electrical energy. However, the amount of power produced using solar energy among the power produced worldwide is negligibly small. Moreover, solar cell efficiency has already reached its limit and solar cell production cost is on the rise. Therefore, there is an increasing need for the implementation of artificial photosynthesis to produce useful materials using sunlight, water and carbon dioxide.

However, despite the efforts made by numerous scientists over the last century, artificial photosynthesis is still not realized even at the laboratory level. For example, Japanese Patent Laid-Open Publication No. 2009-034654 describes a method for producing methane gas by reacting carbon monoxide, carbon dioxide, or a mixture thereof with hydrogen gas in the presence of an iron group transition element. There is a disadvantage in this fall, and the Japanese Patent Laid-Open does not recognize a specific device for implementing artificial photosynthesis. Therefore, the success of research on the device for realizing artificial photosynthesis is expected to make a significant contribution to the improvement of the global environment and the development of science and technology.

The present invention is to solve the above-mentioned problems of the prior art, an object of the present invention to provide a carbon dioxide reduction reaction apparatus and a carbon dioxide reduction method for reducing carbon dioxide by reacting carbon dioxide gas and hydrogen gas using solar energy.

However, the problem to be solved by the present application is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

As a technical means for achieving the above technical problem, a reduction reaction apparatus of carbon dioxide according to the first aspect of the present application, the heat collecting portion for absorbing solar energy; A carbon dioxide reduction reaction unit heated by solar energy; And a reactant supply part and a product discharge part connected to the carbon dioxide reduction reaction part, and hydrogen gas through the reactant supply part into the carbon dioxide reduction reaction part in the presence of a metal catalyst supported on the metal oxide support loaded in the carbon dioxide reduction reaction part. And carbon dioxide gas is injected to react the hydrogen gas with the carbon dioxide gas. The photocatalyst may be in the form of metal particles supported on the metal oxide support, but is not limited thereto.

Reduction apparatus of carbon dioxide according to a second aspect of the present application, the carbon dioxide reduction reaction unit is loaded with a photocatalyst (loading); And a reactant supply part and a product discharge part connected to the carbon dioxide reduction reaction part, and hydrogen gas and carbon dioxide gas are injected into the carbon dioxide reduction reaction part through the reactant supply part to irradiate sunlight in the carbon dioxide reduction reaction part. Under the reaction, the carbon dioxide gas and the hydrogen gas are reacted.

According to one embodiment of the present application, the apparatus for reducing carbon dioxide may further include a reactor for water decomposition, but is not limited thereto.

According to one embodiment of the present application, the water decomposition reactor generates oxygen and hydrogen by decomposition of water by a solar cell, the generated oxygen is removed and the generated hydrogen is supplied into the carbon dioxide reduction reaction unit May be, but is not limited thereto.

According to one embodiment of the present application, the water decomposition reactor converts seawater into freshwater, and produces oxygen and hydrogen by decomposition of the freshwater by solar cells, the generated oxygen is removed and the generated hydrogen is The carbon dioxide reduction may be supplied into the reaction unit, but is not limited thereto.

According to one embodiment of the present application, the reactant supply may include a carbon dioxide gas supply and a hydrogen gas supply, but is not limited thereto.

According to one embodiment of the present application, it may further include a water supply unit connected to the carbon dioxide reduction reaction unit, but is not limited thereto.

According to one embodiment of the present application, the heat collecting portion that absorbs the solar energy may include a solar light collector, but is not limited thereto.

According to one embodiment of the present application, the carbon dioxide reduction reaction unit may include an outer wall in a vacuum state, but is not limited thereto.

According to one embodiment of the present application, the heat collecting portion may be manufactured using a solar absorber or surface treated using a solar absorber, but is not limited thereto. The solar absorbing material may include, for example, one selected from the group consisting of iron oxide, chromium oxide, zirconium oxide, fluoropolymer composition, graphene, graphene oxide, carbon nanotube, graphite, and combinations thereof. However, it is not limited thereto.

According to one embodiment of the present application, the photocatalyst may include, but is not limited to, a metal compound selected from the group consisting of metal oxides, metal carbides, metal oxycarbide, and combinations thereof.

According to one embodiment of the present application, the metal oxide may include an oxide containing one or more metals selected from the group consisting of transition metals, non-transition metals, and combinations thereof, but is not limited thereto.

According to one embodiment of the present application, the metal oxide may include a metal oxide doped by being selected from the group consisting of nonmetallic elements, alkali metals, alkaline earth metals and combinations thereof, but is not limited thereto.

According to one embodiment of the present application, the metal oxide is TiO ₂ , ZnO, Ta ₂ O ₅ , ZrO ₂ , WO ₃ , iron oxide, manganese oxide, copper oxide, cobalt oxide, nickel oxide, chromium oxide, molybdenum oxide, vanadium oxide, indium oxide, lead _{_{_{oxide, ZnCrO 4, ZnFe 2 O 4}}} , MnTiO 3, CaTiO 3, BaTiO 3, SrTiO 3, BiVO 4, Pb 4 Ti 3, CdIn 2 O 4, Fe 2 TiO 5, CrNbO 4, Cr ₂ Ti ₂ O ₇ ; The metal oxide is N, P, As, C, Y, V, Mo, Cr, Cu, Al, Ta, B, Ru, Mn, Fe, Li, Nb, In, Pb, Ge, C, N, S, Doped with Sb or a combination thereof; And combinations thereof, but is not limited thereto.

According to one embodiment of the present application, the metal carbide may include, but is not limited to, carbide of SiC or transition metal.

According to an embodiment of the present disclosure, the metal oxycarbide may include SiOC, or oxycarbide of a transition metal, but is not limited thereto.

According to one embodiment of the present application, the photocatalyst may further include metal particles, but is not limited thereto.

According to one embodiment of the present application, the metal catalyst may be in the form of metal particles, but is not limited thereto.

According to one embodiment of the present application, the metal particles may be of a nanometer size, for example, Fe, Ru, Rh, Co, Ir, Os, Pt, Pd, Ni, Au, Ag, Cu , Co, Zn, Ti, V, Mn, Sn, In, Pb, Cd, Ga and may be selected from the group consisting of, but is not limited thereto.

According to a third aspect of the present invention, there is provided a method of loading a photocatalyst in a carbon dioxide reduction reaction unit including a reactant supply unit; Separating the water into hydrogen gas and oxygen gas in a water decomposition reactor connected to the reactant supply unit including a solar cell; And injecting the hydrogen gas and the carbon dioxide gas into the carbon dioxide reduction reaction unit through the reactant supply unit to react the hydrogen gas and the carbon dioxide gas under solar irradiation.

The fourth aspect of the present invention, the step of loading a photocatalyst in the carbon dioxide reduction reaction unit; Heating the carbon dioxide reduction reaction unit by using solar energy transmitted by a heat collecting unit that absorbs solar energy; And injecting hydrogen gas and carbon dioxide gas into the carbon dioxide reduction reaction unit to react the hydrogen gas with the carbon dioxide gas.

According to the above-mentioned problem solving means of the present application, the carbon dioxide reduction reaction apparatus of the present application can easily reduce carbon dioxide by using sunlight or solar heat.

Carbon dioxide can be easily reduced by heating the carbon dioxide reduction reaction device by solar energy, and liquid fuels such as CO, hydrocarbons, ketones, aldehydes and alcohols can be efficiently produced by the reduction of the carbon dioxide. In particular, the heat collecting portion of the carbon dioxide reduction device is manufactured by the solar absorber or surface treatment using the solar absorber can effectively absorb the sunlight and convert it into thermal energy, carbon dioxide reduction of the carbon dioxide reduction device The temperature of the reaction portion can be easily increased to a temperature at which carbon dioxide can be reduced. Accordingly, by using the carbon dioxide reduction reaction apparatus according to the present application can improve the efficiency of the production process of the fuel material through the reduction of carbon dioxide and contribute to the practical use.

Moreover, carbon dioxide can be easily reduced by using a photocatalyst, and liquid fuels, such as CO, a hydrocarbon, ketones, aldehydes, and alcohols, can be manufactured efficiently by the said carbon dioxide reduction. In particular, since hydrogen for reducing carbon dioxide is generated by decomposition of water by a solar cell, there is no concern about environmental pollution, and further reduction of the carbon dioxide may be further improved by adding water in the process of reducing carbon dioxide. Accordingly, by using the carbon dioxide reduction reaction apparatus according to the present application can improve the efficiency of the production process of the fuel material through the reduction of carbon dioxide and contribute to the practical use.

1 is a schematic diagram of a carbon dioxide reduction reaction apparatus according to an embodiment of the present application.

2 is a schematic view of a carbon dioxide reduction reaction apparatus according to an embodiment of the present application.

3 is a schematic view of a carbon dioxide reduction reaction apparatus according to an embodiment of the present application.

4 is a schematic view of a carbon dioxide reduction reaction apparatus according to an embodiment of the present application.

5 is a schematic diagram of a carbon dioxide reduction reaction apparatus according to an embodiment of the present application.

6 is a schematic view of a carbon dioxide reduction reaction apparatus according to an embodiment of the present application.

7 is a schematic diagram of a carbon dioxide reduction reaction apparatus according to an embodiment of the present application.

DETAILED DESCRIPTION Hereinafter, embodiments and examples of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted for simplicity of explanation, and like reference numerals designate like parts throughout the specification.

Throughout this specification, when a portion is "connected" to another portion, this includes not only "directly connected" but also "electrically connected" with another element in between. do.

Throughout this specification, when a member is located “on” another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless specifically stated otherwise. As used throughout this specification, the terms "about", "substantially" and the like are used at, or in the sense of, numerical values when a manufacturing and material tolerance inherent in the stated meanings is indicated, Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers. As used throughout this specification, the term "step to" or "step of" does not mean "step for."

Throughout this specification, the term “combination of these” included in the expression of the makushi form means one or more mixtures or combinations selected from the group consisting of the constituents described in the expression of the makushi form, wherein the constituents It means to include one or more selected from the group consisting of.

With reference to Figures 1 to 4 will be described in detail the carbon dioxide reduction reaction apparatus and the carbon dioxide reduction method according to an embodiment of the present application.

Reduction device of carbon dioxide according to an embodiment of the present application, the heat collecting unit 100 for absorbing solar energy, the carbon dioxide reduction reaction unit 200 is heated by the solar energy, and the carbon dioxide reduction reaction unit 200 The reactant feeder 300 and the product outlet 400 may be included (see FIG. 1).

Sunlight is incident through the heat collecting part 100. The heat collecting unit 100 may be directly connected to the carbon dioxide reduction reaction unit 200, for example, may be disposed on the front surface of the carbon dioxide reduction reaction unit 200, but is not limited thereto. The heat collecting unit 100 may not be directly connected to the carbon dioxide reduction reaction unit 200, but may be separated. In this case, the carbon dioxide reduction reaction unit 200 may be absorbed by the heat collecting unit 100. It can be heated by taking heat. For example, the heat collecting part 100 may include a solar light collector (not shown) for condensing sunlight, but is not limited thereto. The solar collector is not limited in shape or material as long as it is an article capable of efficiently collecting sunlight. The shape may be, for example, a flat plate, a trough type, a parabola type, and the like, and the material may include glass, silicon, a thermoplastic film, a thermosetting film, and the like, but is not limited thereto.

The heat collecting part 100 may perform a function of a heating part that absorbs solar thermal energy from incident sunlight and heats the carbon dioxide reduction reaction part 200. In one embodiment of the present application, in order to efficiently absorb solar energy, the heat collecting part 100 may be painted in black, but is not limited thereto. In addition, in order to increase the contact area with sunlight, the heat collecting part 100 may be, for example, having an uneven shape, but is not limited thereto.

The heat collecting part 100 may be manufactured using a solar absorbing material or may be surface treated using a solar absorbing material, but is not limited thereto. As sunlight is absorbed by the solar absorbing material, the temperature of the heat collecting part 100 may be increased. The solar absorbing material may be used without limitation as long as the material absorbs sunlight and converts it into thermal energy easily. For example, the solar absorbing material may be iron oxide, chromium oxide, zirconium oxide, or fluoropolymer composition. , Graphene, graphene oxide, carbon nanotubes, graphite, and may include those selected from the group consisting of, but is not limited thereto.

As the heat collecting part 100 absorbs solar energy and is heated, the carbon dioxide reduction reaction part 200 may be simultaneously heated. The carbon dioxide reduction reaction unit 200 may be heated to a temperature at which carbon dioxide gas is reduced by reacting with hydrogen gas. For example, the carbon dioxide reduction reaction unit 200 may be heated to about 100 ° C. or more, about 150 ° C. or more, about 200 ° C. or more, about 250 ° C. or more, or about 300 ° C. or more, about 1000 ° C. or less, or about 950 ° C. Or less, about 900 degrees C or less, about 850 degrees C or less, or about 800 degrees C or less, but is not limited thereto.

The heated carbon dioxide reduction reaction unit 200 may decrease in temperature due to contact with air. In order to maintain the internal temperature of the carbon dioxide reduction reaction unit 200 to a predetermined level or more, the carbon dioxide reduction reaction unit 200 may be surrounded by an outer wall 220 to block contact with the outside air. The inner space of the outer wall 220 may be a vacuum state, but is not limited thereto. When the inner space of the outer wall 220 is in a vacuum state, the temperature of the carbon dioxide reduction reaction unit 200 may be maintained at a high temperature for a long time due to the excellent heat insulating effect of the vacuum. The outer wall 220 may be an outer surface painted in black so as to easily absorb light, but is not limited thereto (see FIG. 2).

Hydrogen gas and carbon dioxide gas are injected through the reactant supply unit 300. The hydrogen gas and carbon dioxide gas are reacted in the presence of a metal catalyst supported on the metal oxide support loaded in the carbon dioxide reduction reaction unit 200, and the carbon dioxide gas is reduced by the reaction to CO, hydrocarbons, ketones, aldehydes, Liquid fuels such as alcohols may be produced, but are not limited thereto. The generated liquid fuel may be discharged through the product discharge unit 400.

The reactant supply unit 300 may include a hydrogen gas supply unit 310 and a carbon dioxide gas supply unit 320 (see FIG. 2). The hydrogen gas may be supplied to the carbon dioxide reduction reaction unit 200 through the hydrogen gas supply unit 310, and the carbon dioxide gas may be supplied to the carbon dioxide reduction reaction unit 200 through the carbon dioxide gas supply unit 320. Can be. The hydrogen gas and the carbon dioxide gas supplied into the carbon dioxide reduction reaction unit 200 may be each independently supplied or pre-mixed, but are not limited thereto.

The reactant supply unit 300 may further include a water supply unit 330. By additionally supplying water to the carbon dioxide reduction reaction unit 200 by the water supply unit 330, the hydrogen gas and the carbon dioxide gas may react more easily. In addition, the amount of the water supplied may be greater than about 0 ppm to about 100 ppm based on the total volume of the hydrogen gas and the carbon dioxide gas supplied to the carbon dioxide reduction reaction unit 200, but is not limited thereto. . The additionally supplied water may be injected into the carbon dioxide reduction reaction unit 200 or supplied in the form of water vapor, but is not limited thereto.

The hydrogen gas supply unit 310 may be connected to the reactor 500 for water decomposition, but is not limited thereto. The water decomposition reactor may include a solar cell 510, a water decomposition reactor 520, and a separation unit (not shown) connected to the water decomposition reactor, and the separation unit may include a hydrogen gas discharge unit 531. ) And an oxygen gas discharge part 532, and the hydrogen gas discharge part 531 may be connected to the hydrogen gas supply part 310, but is not limited thereto (see FIGS. 3 and 4). ).

In the water decomposition reactor 520, the water 523 is electrolyzed by the solar cell 510 to generate hydrogen gas and oxygen gas. The generated hydrogen gas is discharged by the hydrogen discharge unit 531, and the discharged hydrogen gas is supplied to the hydrogen gas supply unit 310.

Specifically, sunlight is irradiated to the solar cell 510 of the water decomposition reactor 500 to generate photovoltaic power from the solar cell 510. The generated photovoltaic power is applied to the water 523 by the first electrode 521 and the second electrode 522, whereby the water 523 is hydrogen ions (H ⁺ ) and oxygen ions (O ^{2 −).} Decompose into At the same time, the oxygen ions are oxidized on the surface of the second electrode 522 to generate oxygen gas (O ₂ ). The generated oxygen gas may be discharged to the atmosphere by the oxygen gas discharge unit 532. The hydrogen ions move to the first electrode 521, and the hydrogen ions are reduced on the surface of the first electrode 521 to generate hydrogen gas. The generated hydrogen gas is discharged by the hydrogen gas discharge part 531 and supplied to the hydrogen gas supply part 310.

For example, the water decomposition reactor may include a photocatalyst, a water decomposition reactor, and a separation unit connected to the water decomposition reactor, and the photocatalyst may be formed in the water decomposition reactor, and the separation unit A hydrogen gas discharge unit and an oxygen gas discharge unit may be included, and the hydrogen gas discharge unit may be connected to the hydrogen gas supply unit, but is not limited thereto. In the water decomposition reactor, water may be separated into hydrogen and oxygen by the photocatalyst. The hydrogen and oxygen are formed in the form of a mixed gas, and may be separated into a hydrogen gas outlet and an oxygen gas outlet through predetermined separation processes, respectively. The separation process is not limited, and for example, separation by a porous separator, separation by a capillary condensate flow, etc. may be used, but is not limited thereto. The photocatalyst is not limited, and may be, for example, a titanium compound, a zinc compound, a sulfide compound, a niobium compound, or a combination thereof, but is not limited thereto.

According to one embodiment of the present application, the reactor 500 for water decomposition may further include a desalination apparatus (not shown) of seawater. Accordingly, the water 523 may be seawater, and the seawater may be converted into freshwater by a desalination apparatus (not shown) of the seawater, and the hydrogenated water and oxygen gas may be generated by electrolyzing the freshwater.

The seawater desalination device (not shown) may desalination of seawater by reverse osmosis or evaporation, but is not limited thereto. For example, the desalination device of seawater (not shown) may be evaporated to vaporize seawater. The unit may include a condensation unit for liquefying evaporated water vapor, a solar heat collecting unit, and a heat storage tank storing solar heat. In the seawater desalination apparatus (not shown), the seawater is heated while circulating inside the heat storage tank heated by the solar energy absorbed by the solar heat collecting portion. The heated sea water is evaporated in the evaporator to form water vapor, and the water vapor may be liquefied in the condensation part to be converted into fresh water.

The hydrogen gas and the carbon dioxide gas supplied to the carbon dioxide reduction reaction unit 200 react in the presence of a metal catalyst supported on the metal oxide support loaded in the carbon dioxide reduction reaction unit 200, and the carbon dioxide gas is reacted by the reaction. It can be reduced to produce liquid fuels such as CO, hydrocarbons, ketones, aldehydes, alcohols and the like. The reaction in the carbon dioxide reduction reaction unit 200 may be, for example, represented by Schemes 1 and 2 below, but is not limited thereto.

Scheme 1

CO ₂ + 4H ₂ → CH ₄ + 2H ₂ O

Scheme 2

CO ₂ + H ₂ → CO + H ₂ O (first reaction)

CO + 2H ₂ → CH ₃ OH (second catalytic reaction)

According to the exemplary embodiment of the present application, the metal catalyst may be supported on the metal oxide support in the form of particles, and the metal catalyst may be in the form of particles having a size in nanometers, but is not limited thereto. . For example, the metal catalyst may include one selected from the group consisting of Pt, Pd, Ni, Au, Ag, Cu, Ru, Rh, Ir, Fe, and combinations thereof, but is not limited thereto. no.

According to the exemplary embodiment of the present disclosure, the metal oxide support may be in the form of particles having a size of nanometers to micrometers, and may have pores in nanometers, but is not limited thereto. . The metal oxide support may be, for example, a mesoporous structure, a rod, a fiber, or a tube, but is not limited thereto.

For example, the metal oxide may include an oxide containing at least one metal selected from the group consisting of transition metals, non-transition metals, and combinations thereof; Alternatively, the metal oxide may include a metal oxide doped by being selected from the group consisting of nonmetal elements, alkali metals, alkaline earth metals, and combinations thereof, but is not limited thereto. For example, the metal oxide may be a metal oxide that absorbs light in a region including visible light, ultraviolet light, infrared light, or a combination thereof, but is not limited thereto. Non-limiting examples of the metal oxides include TiO ₂ , ZnO, Ta ₂ O ₅ , ZrO ₂ , WO ₃ , iron oxides, manganese oxides, copper oxides, cobalt oxides, nickel oxides, chromium oxides, molybdenum oxides, vanadium oxides, and indium oxides. , lead _{_{_{oxide, ZnCrO 4, ZnFe 2 O 4}}} , MnTiO 3, CaTiO 3, BaTiO 3, SrTiO 3, BiVO 4, Pb4Ti 3, CdIn 2 O 4, Fe 2 TiO 5, CrNbO 4, Cr 2 Ti 2 O 7; The metal oxide is N, P, As, C, Y, V, Mo, Cr, Cu, Al, Ta, B, Ru, Mn, Fe, Li, Nb, In, Pb, Ge, C, N, S, Doped with Sb or a combination thereof; And it may include those selected from the group consisting of, but is not limited thereto.

5 to 7 will be described in detail with respect to the carbon dioxide reduction reaction apparatus and the carbon dioxide reduction method according to an embodiment of the present application.

In the carbon dioxide reduction reaction device according to the exemplary embodiment of the present disclosure, the carbon dioxide reduction reaction unit 200 in which the photocatalyst 210 is loaded is connected to the reactant supply unit 300, and water decomposition including a solar cell 510 is performed. Reactor 500 may be connected to the reactant supply 300, and may further include a product discharge 400 (see Figure 5).

The water decomposition reactor 500 includes water. The solar cell 510 included in the water decomposition reactor 500 is operated by solar incidence, and water is separated into hydrogen gas and oxygen gas by a current generated by the solar cell 510. The separated hydrogen gas is injected into the carbon dioxide reduction reaction unit 200 through the reactant supply unit 300, and carbon dioxide gas is injected into the carbon dioxide reduction reaction unit 200 by the reactant supply unit 300. . The hydrogen gas and carbon dioxide gas react in the presence of the photocatalyst 210 loaded inside the carbon dioxide reduction reaction unit 200, and the carbon dioxide gas is reduced to reduce CO, hydrocarbons, ketones, aldehydes, alcohols, and the like. Liquid fuel may be produced, but is not limited thereto. The generated liquid fuel may be discharged through the product discharge unit 400. The reaction in the carbon dioxide reduction reaction unit 200 may be, for example, represented by Schemes 1 and 2 below, but is not limited thereto.

Scheme 1

CO ₂ + 4H ₂ → CH ₄ + 2 H ₂ O

Scheme 2

CO ₂ + H ₂ → CO + H ₂ O (first reaction)

CO + 2H ₂ → CH ₃ OH (second catalytic reaction)

The solar cell 510 may be connected to the first electrode 521 and the second electrode 522, and the first electrode 521 and the second electrode 522 may be connected to the water 523. The water 523 may be separated into hydrogen gas and oxygen gas (see FIG. 6). Specifically, sunlight is irradiated to the solar cell 510 of the water decomposition reactor 500 to generate photovoltaic power from the solar cell 510. The generated photovoltaic power is applied to the water 523 by the first electrode 521 and the second electrode 522, whereby the water 523 is hydrogen ions (H ⁺ ) and oxygen ions (O ^2). It is decomposed ^into). At the same time, the oxygen ions are oxidized on the surface of the second electrode 522 to generate oxygen gas (O ₂ ). The generated oxygen gas may be discharged to the atmosphere or collected separately for use in other applications. The hydrogen ions move to the first electrode 521, and the hydrogen ions are reduced on the surface of the first electrode 521 to generate hydrogen gas. The solar cell 510 is not limited, and may be, for example, a silicon solar cell, a dye-sensitized solar cell, a compound semiconductor solar cell, an organic molecular junction solar cell, or the like, but is not limited thereto.

According to one embodiment of the present application, the water decomposition reactor 500 may be connected to a converter (not shown) for converting seawater into fresh water, and the water 523 is converted in the converter (not shown) It may be fresh water, but is not limited thereto. The converter (not shown) may desalination of seawater by reverse osmosis or evaporation, but is not limited thereto. For example, the converter (not shown) may include an evaporator for vaporizing seawater, a condenser for liquefying evaporated water vapor, a solar heat collecting unit, and a heat storage tank for storing solar heat. In the converter (not shown), the sea water is heated while circulating inside the heat storage tank heated by the solar energy absorbed by the solar heat collecting portion. The heated sea water is evaporated in the evaporator to form water vapor, and the water vapor may be liquefied in the condensation part to be converted into fresh water. Fresh water converted in the converter may be injected into the water decomposition reactor.

According to an embodiment of the present disclosure, the reactant supply unit 300 may further include a carbon dioxide gas supply unit 320 and a water supply unit 330 (see FIG. 7). Carbon dioxide gas may be injected into the carbon dioxide reduction reaction unit 200 by the carbon dioxide gas supply unit, and may react with hydrogen gas under the photocatalyst 210. By additionally supplying water to the carbon dioxide reduction reaction unit 200 by the water supply unit 330, the hydrogen gas and the carbon dioxide gas may react more easily. In addition, the amount of the water supplied may be greater than about 0 ppm to about 100 ppm based on the total volume of the hydrogen gas and the carbon dioxide gas supplied to the carbon dioxide reduction reaction unit 200, but is not limited thereto. . The additionally supplied water may be injected into the carbon dioxide reduction reaction unit 200 or supplied in the form of water vapor, but is not limited thereto.

The photocatalyst 210 may be any photocatalyst known in the art and a catalytic material having a reducing activity of carbon dioxide under light irradiation without particular limitation. The photocatalyst 210 may include, for example, a metal compound, but is not limited thereto.

According to the exemplary embodiment of the present application, the metal compound may be, for example, one selected from the group consisting of metal oxides, metal carbides, metal oxycarbide, and combinations thereof, but is not limited thereto. . The metal oxide may include an oxide containing one or more metals selected from the group consisting of transition metals, non-transition metals, and combinations thereof, and include nonmetallic elements, alkali metals, alkaline earth metals, and combinations thereof. It may be doped by being selected from the group consisting of, but is not limited thereto. For example, the metal oxide is TiO ₂ , ZnO, Ta ₂ O ₅ , ZrO ₂ , WO ₃ , iron oxide, manganese oxide, copper oxide, cobalt oxide, nickel oxide, chromium oxide, molybdenum oxide, vanadium oxide, indium oxide , lead _{_{_{oxide, ZnCrO 4, ZnFe 2 O 4}}} , MnTiO 3, CaTiO 3, BaTiO 3, SrTiO 3, BiVO 4, Pb 4 Ti 3, CdIn 2 O 4, Fe 2 TiO 5, CrNbO 4, Cr 2 Ti 2 O ₇ ; The metal oxide is N, P, As, C, Y, V, Mo, Cr, Cu, Al, Ta, B, Ru, Mn, Fe, Li, Nb, In, Pb, Ge, C, N, S, Doped with Sb or a combination thereof; And combinations thereof, but is not limited thereto.

The metal carbide may include a carbide of SiC or a transition metal, and the metal oxycarbide may include an oxycarbide of SiOC or a transition metal, but is not limited thereto.

According to the exemplary embodiment of the present application, the photocatalyst 210 may further include metal particles, but is not limited thereto. The metal particles may have a size in nanometers, the metal particles, for example, Fe, Ru, Rh, Co, Ir, Os, Pt, Pd, Ni, Au, Ag, Cu, Co, Zn, Ti, V, Mn, Sn, In, Pb, Cd, Ga and may be to include those selected from the group consisting of, but is not limited thereto.

The foregoing description of the application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above description, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present application.

Claims

A collector for absorbing solar energy;

A carbon dioxide reduction reaction unit heated by solar energy; And,

Reactant supply unit and product discharge unit connected to the carbon dioxide reduction reaction unit

Including;

Hydrogen gas and carbon dioxide gas are injected into the carbon dioxide reduction reaction unit through the reactant supply unit in the presence of a metal catalyst supported on the metal oxide support loaded in the carbon dioxide reduction reaction unit to react the hydrogen gas and the carbon dioxide gas. ,

Reduction reaction apparatus of carbon dioxide.
A carbon dioxide reduction reaction unit in which a photocatalyst is loaded; And,

Reactant supply unit and product discharge unit connected to the carbon dioxide reduction reaction unit

Including;

Hydrogen gas and carbon dioxide gas are injected into the carbon dioxide reduction reaction unit through the reactant supply unit to react the carbon dioxide gas and the hydrogen gas under solar irradiation in the carbon dioxide reduction reaction unit.

Reduction reaction apparatus of carbon dioxide.
The method according to claim 1 or 2,

Reduction reaction apparatus for carbon dioxide, further comprising a reactor for water decomposition.
The method of claim 3, wherein

The reactor for water decomposition generates oxygen and hydrogen by decomposition of water by a solar cell, the generated oxygen is removed and the generated hydrogen is supplied to the carbon dioxide reduction reaction unit, carbon dioxide reduction reaction apparatus.
The method of claim 3, wherein

The reactor for water decomposition converts seawater into freshwater, and produces oxygen and hydrogen by decomposition of the freshwater by solar cells, the generated oxygen is removed and the generated hydrogen is supplied into the carbon dioxide reduction reaction unit. The reduction reaction apparatus of carbon dioxide.
The method according to claim 1 or 2,

The reactant supply unit will include a carbon dioxide gas supply unit and a hydrogen gas supply unit, carbon dioxide reduction reaction apparatus.
The method according to claim 1 or 2,

Reducing reaction apparatus of carbon dioxide that further comprises a water supply unit connected to the carbon dioxide reduction reaction unit.
The method of claim 1,

The heat collecting unit for absorbing the solar energy will include a solar collector, carbon dioxide reduction reaction device.
The method of claim 1,

The carbon dioxide reduction reaction unit that includes a vacuum outer wall, carbon dioxide reduction reaction apparatus.
The method of claim 1,

The heat collecting unit is manufactured using a solar absorber or surface treated using a solar absorber, carbon dioxide reduction reaction apparatus.
The method of claim 10,

The photovoltaic material includes iron oxide, chromium oxide, zirconium oxide, fluorine polymer composition, graphene, graphene oxide, carbon nanotubes, graphite, and those selected from the group consisting of a combination of carbon dioxide, Reduction reaction apparatus.
The method of claim 2,

The photocatalyst comprises a metal compound selected from the group consisting of metal oxides, metal carbides, metal oxycarbide, and combinations thereof.
The method of claim 1 or 12,

Wherein the metal oxide comprises a oxide containing at least one metal selected from the group consisting of transition metals, non-transition metals and combinations thereof, carbon dioxide reduction reaction apparatus.
The method of claim 1 or 12,

The metal oxide comprises a metal oxide doped by being selected from the group consisting of non-metal elements, alkali metals, alkaline earth metals and combinations thereof, reduction apparatus of carbon dioxide.
The method of claim 1 or 12,

The metal oxide is TiO 2 , ZnO, Ta 2 O 5 , ZrO 2 , WO 3 , iron oxide, manganese oxide, copper oxide, cobalt oxide, nickel oxide, chromium oxide, molybdenum oxide, vanadium oxide, indium oxide, lead oxide, ZnCrO 4, ZnFe 2 O 4 , MnTiO 3 , CaTiO 3 , BaTiO 3, SrTiO 3 , BiVO 4 , Pb 4 Ti 3 , CdIn 2 O 4 , Fe 2 TiO 5 , CrNbO 4 , Cr 2 Ti 2 O 7 ; The metal oxide is N, P, As, C, Y, V, Mo, Cr, Cu, Al, Ta, B, Ru, Mn, Fe, Li, Nb, In, Pb, Ge, C, N, S, Doped with Sb or a combination thereof; And a combination selected from the group consisting of combinations thereof.
The method of claim 12,

Wherein the metal carbide comprises a carbide of SiC or transition metal, carbon dioxide reduction reaction apparatus.
The method of claim 12,

The metal oxycarbide is SiOC, or a reduction reaction device of carbon dioxide comprising a oxycarbide of transition metal.
The method of claim 2,

The photocatalyst further comprises a metal particle, carbon dioxide reduction reaction apparatus.
The method of claim 1,

The metal catalyst is in the form of metal particles, carbon dioxide reduction reaction apparatus.
The method of claim 18 or 19,

The metal particles are Fe, Ru, Rh, Co, Ir, Os, Pt, Pd, Ni, Au, Ag, Cu, Co, Zn, Ti, V, Mn, Sn, In, Pb, Cd, Ga and their Reducing reaction apparatus for carbon dioxide, comprising one selected from the group consisting of combinations.
Loading a photocatalyst into a carbon dioxide reduction reaction unit including a reactant supply unit;

Separating the water into hydrogen gas and oxygen gas in a water decomposition reactor connected to the reactant supply unit including a solar cell; And

Injecting the hydrogen gas and the carbon dioxide gas into the carbon dioxide reduction reaction unit through the reactant supply unit to react the hydrogen gas and the carbon dioxide gas under solar irradiation

Reducing the carbon dioxide comprising a.
Loading a photocatalyst into the carbon dioxide reduction reaction unit;

Heating the carbon dioxide reduction reaction unit by using solar energy delivered by a heat collecting unit that absorbs solar energy; And

Reacting the hydrogen gas and the carbon dioxide gas by injecting hydrogen gas and carbon dioxide gas into the carbon dioxide reduction reaction unit;

Reducing the carbon dioxide comprising a.